Copper-catalyzed oxidative esterification of alcohols with aldehydes activated by Lewis acids

An efficient oxidative esterification of aromatic and aliphatic aldehydes with simple alcohols was accomplished using catalytic amounts of Cu(ClO₄)₂·6H₂O and InBr₃ with tert-hydroperoxide as an oxidant.     

Synthesis,thermal analysis,and linear and nonlinear optical characterization of substituted polyphosphonates derived from 1,12‐dodecanediol

The syntheses of a series of substituted polyphosphonates of the type [OP(X)(Ar)O(CH₂)₁₂]_n (X = O, S, Se; Ar = phenyl, 2,2′‐bithienyl‐5‐yl) are reported. The s for the polyphosphonates range from 1.1 to 4.6 × 10⁴ Da and are significantly higher than those previously reported for polyphosphonates synthesized via polycondensation reactions. Thermal characterization indicates that all of the polymers are in the rubbery state at room temperature and have thermal stabilities as high as 290 °C. The linear absorption spectra, emission spectra, and emission quantum yields of the 2,2′‐bithenyl‐5‐yl substituted polyphosphonates show distinct trends with respect to the chalcogen attached to the phosphorus. Solutions of these polymers show emission at wavelengths ranging from 380 to 400 nm and, depending on the choice of X, the quantum yields are considerably larger than that of 2,2′‐bithiophene. Nonlinear optical measurements of the polyphosphonates with 2,2′‐bithenyl‐5‐yl substituents show that nonlinear absorbance increases with increasing molecular weight of X. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3663–3674     

Syntheses of aliphatic polyesters catalyzed by lanthanide triflates

Polycondensations of 1,6‐hexane diol and sebacic acid were conducted in bulk with addition of a lanthanide triflate as acidic catalyst. With exception of promethium triflate all lanthanide triflates were studied. A particularly low molecular weight was obtained with neodym triflate and the best results with samarium triflate. With Sm(OTf)₃ weight average (M_w) values up to 65 kDa (uncorrected SEC data) were achieved after optimization of the reaction conditions. Comparison of these results with those obtained from bismuth, magnesium, and zinc triflates, on the one hand, and comparison with the acidities of all catalysts, on the other, indicates that the esterification mechanism involves complexation of monomer by metal ions. Preparation of multiblock copoly(ether ester)s failed due to insufficient incorporation of poly(tetrahydrofuran) diols. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 170–177, 2009     

Synthesis and characterization of postsulfonated poly(arylene ether sulfone) diblock copolymers for proton exchange membranes

Sulfonated poly(arylene ether sulfone) diblock copolymers were studied through the postsulfonation process. Two kinds of hydrophobic oligomers with a molecular weight of 20 kDa were prepared in advance as block sequences and then coupled together to obtain diblock copolymers. One oligomer was synthesized from bis(4‐hydroxyphenyl) sulfone (BHPS) and 4,4′‐difluorodiphenyl sulfone (DFDPS), which was thought to be incapable of postsulfonation. The other oligomer was synthesized from hydroquinone (HQ) and 4,4′‐dichlorodiphenyl sulfone (DCDPS), which successfully proceeded to a hydrophilic sequence as a result of sulfonation onto the HQ moiety after the coupling reaction. Consequently, a diblock copolymer with high molecular weight was obtained; although its intrinsic viscosity was too low to form a tough membrane because of its high rigidity and high crystallinity. Therefore, the use of decafluorobiphenyl (10F) as a termination reagent was investigated with the aim of achieving higher coupling reactivity and a kinky property. As a result, a sulfonated diblock copolymer was successfully obtained with sufficient molecular weight and intrinsic viscosity to form the membrane, as well as with adequate thermal properties. It was observed that proton conductivity, water uptake, and the water diffusion coefficient increased with higher ion exchange capacity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 700–712, 2009     

A convenient room temperature polycondensation toward hyperbranched AB2‐type all‐aromatic polyesters with phenol terminal groups

As a convenient alternative to the classical melt polycondensation the one‐pot solution polycondensation of suitable AB₂ monomers under mild conditions has been successfully adapted to hyperbranched all‐aromatic polyester with phenol terminal groups. The polymerization was performed in solution at room temperature directly using commercially available 3,5‐dihydroxybenzoic acid as monomer and 4‐(dimethylamino) pyridinium 4‐tosylate as catalyst to suppress the formation of N‐acylurea. Different carbodiimides as coupling agents were investigated to find the optimal esterification conditions. The polymers have been characterized extensively and were compared with their well‐known analogs synthesized in melt. The characterization was carried out by NMR spectroscopy, size exclusion chromatography, and asymmetric flow‐field flow fractionation as an alternative separation technique for multifunctional polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5158–5168, 2009     

Silica/Polyamide Nanocomposite Synthesis via an Original Double Emulsification Process in Miniemulsion

Summary: A new method for the encapsulation of inorganic charges by an organic polymer by a reactive double emulsification process is proposed. This work is especially novel since it is highly unusual to encounter polymerization reactions in such a double emulsification process. Silica was first synthesized in cyclohexane using a sol–gel process in an inverse microemulsion in the presence of a non‐ionic surfactant (nonylphenyl ether polyoxyethylene), tetraethoxysilane, and concentrated ammonia. The coupling agent, 3‐aminopropyl triethoxysilane, was then grafted onto the surface of the silica nanoparticles. In a third step, direct miniemulsions were prepared from the microemulsion containing the functionalized silica nanoparticles. The miniemulsions were prepared using sodium dodecylsulfate as the surfactant and cetyl alcohol as the costabilizer. Finally, an interfacial polycondensation occurred between a diamine added to the external phase and sebacoyl chloride in solution in the dispersed phase. The formation of polyamide latexes was proven using infrared spectroscopy, and observation of the nanocomposites by transmission electron microscopy showed mean diameters of 100 nm.

TEM micrograph of silica/polyamide nanocomposite particles     

Synthesis of high refractive‐index melt‐stable aromatic polyphosphonates

The synthesis of aromatic polyphosphonates based on the step polymerization of various bisphenols and dichlorophenyl phosphine oxide was investigated. The effect of catalyst, type, concentration, and polymerization time were systematically varied to obtain high molecular weight polymers. Very high molecular weight tough, ductile materials with a high degree of optical clarity were synthesized. In contrast with the aromatic polycarbonates, the refractive index was increased from 1.58 to 1.60 (for the bisphenol A‐based system) and 1.64 for a biphenol‐based system. The latter was still an amorphous soluble polymer as a result of the non‐coplanar nature of the phenyl phosphine oxide bond, unlike the analogous polycarbonate. Hydrolytically stable melt‐processable cumyl phenol end‐capped polyphosphonates were successfully achieved for the first time. Rheological studies show that these end‐capped systems are melt‐stable at 200 °C, whereas the systems of initially higher molecular weight but without any well‐defined end capping clearly degraded quickly probably as a result of an acid‐catalyzed hydrolysis process. Extensive high char yields were produced upon pyrolysis in either nitrogen or air, suggesting good fire resistance. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2904–2910, 2001     

Na-W-Mn/SiO2催化剂中的金属-载体作用

研究了Na-W-Mn/SiO₂催化剂中不同活性组份对载体结构的影响.结果表明,Na的诱导作用使无定型氧化硅在焙烧过程中相变为α-方石英结构,同时伴有比表面积的大幅度下降;单独担载Na时,硅小球经焙烧后基本无微孔存在,担载W则能使硅小球焙烧后形成较为均一的微米孔道.SiO₂载体在Na和W作用下发生的结构变化对催化剂的选择性起重要作用.     

New mechanistic insights on Justicia vahlii Roth: UPLC-Q-TOF-MS and GC–MS based metabolomics,in-vivo,in-silico toxicological,antioxidant based anti-inflammatory and enzyme inhibition evaluation

Justicia vahlii Roth. (acanthaceae) is an important medicinal food plant used in pain relief and topical inflammation. The present study aimed to evaluate phytochemical composition, toxicity, anti-inflammatory, antioxidant and enzyme inhibition potential of n-butanol extract of J. vahlii (BEJv). The extract prepared through maceration was found rich in total phenolic contents (TPC) 196.08 ± 6.01 mg of Gallic acid equivalent (mg GAE/g DE) and total flavonoid contents (TFC) 59.08 ± 1.32 mg of Rutin equivalent (mg RE/g DE). The UPLC-Q-TOF-MS analysis of BEJv showed tentative identification of 87 compounds and 19 compounds were detected in GC–MS analysis. The HPLC-PDA quantification showed the presence of 14 polyphenols amongst which kaempferol (3.45 ± 0.21 µg/ mL DE) and ferulic acid (2.31 ± 1.30 µg/ mL DE) were found in highest quantity. The acute oral toxicity study revealed the safety and biocompatibility of the extract up to 3000 mg/kg in mice. There was no effect of BEJv on human normal liver cells (HL 7702) and very low cytotoxic effect on liver cancer cells (HepG2) and breast cancer cells (MCF-7). In anti-inflammatory evaluation, the BEJv treated groups showed significant inhibition (p < 0.001) of late phase carrageenan induced paw edema at 400 mg/kg and increased the levels of oxidative stress markers; catalase, superoxide dismutase (SOD) and glutathione (GSH) while decreased the inflammatory markers; interleukin-1beta (IL-β) and tumor necrosis factor alpha (TNF-α) in paw tissue of mice. BEJv displayed highest results in Ferric reducing antioxidant power (FRAP) assay 97. 21 ± 2.34 mg TE (trolox equivalent)/g DE, and highest activity 3.32 ± 0.31 mmol ACAE (acarbose equivalent)/g D.E against α-glucosidase. Docking study showed good docking score by the tested compounds against the various clinically significant enzymes. Conclusively the current study unveiled J. vahlii as novel non-toxic source with good antioxidant-mediated anti-inflammatory potential which strongly back the traditional use of the species in pain and inflammation.